Stable formulated systems with chloro-3,3,3-trifluoropropene

ABSTRACT

The present invention relates to formulated refrigerant systems of 1-chloro-3,3,3-trifluoropropene (R-1233zd) that are sufficiently thermally and chemically stable such that they can be effectively used sans additional stabilizers. The formulations of the present invention are particularly useful compositions for refrigeration, heat transfer and foam blowing.

This application is a continuation application of U.S. application forpatent Ser. No. 13/738,211 filed Jan. 10, 2013 which claims priority toU.S. application for patent Ser. No. 12/667,121 filed Dec. 29, 2009,abandoned, which claims priority to International application for patentSerial Number PCT/US2009/036267 filed Mar. 6, 2009 which designated theUnited States, which claimed priority to U.S. provisional applicationfor patent Ser. No. 61/034,513 filed Mar. 7, 2008.

FIELD OF THE INVENTION

The present invention relates to formulated systems of1-chloro-3,3,3-trifluoropropene (R-1233zd) and/or2-chloro-3,3,3-trifluoropropene (R-1233xf) that are sufficientlythermally and chemically stable such that they can be effectively usedwithout the need for additional stabilizers. The formulations of thepresent invention are particularly useful compositions forrefrigeration, heat transfer, and foam pre-mixes.

BACKGROUND OF THE INVENTION

With continued regulatory pressure there is a growing need to identifymore environmentally sustainable replacements for refrigerants, heattransfer fluids, foam blowing agents, solvents, and aerosols with lowerozone depleting and global warming potentials. Chlorofluorocarbon (CFC)and hydrochlorofluorocarbons (HCFC), widely used for these applications,are ozone depleting substances and are being phased out in accordancewith guidelines of the Montreal Protocol. Hydrofluorocarbons (HFC) are aleading replacement for CFCs and HCFCs in many applications. Though theyare deemed “friendly” to the ozone layer they still generally possesshigh global warming potentials. One new class of compounds that has beenidentified to replace ozone depleting or high global warming substancesare halogenated olefins, such as hydrofluoroolefins (HFO) andhydrochlorofluoroolefins (HCFO). Because of the presence of alkenelinkage it is expected that the HFOs and HCFOs will be chemicallyunstable, relative to HCFCs or CFCs. The inherent chemical instabilityof these materials in the lower atmosphere results in short atmosphericlifetimes, which provide the low global warming potential and zero ornear zero ozone depletion properties desired. However, such inherentinstability is believed to also impact the commercial application ofsuch materials, which may degrade during storage, handling and use.

WO 2009/003165 discloses stabilized formulations of HFOs and HCFOs in avariety of applications and compositions. This patent applicationdiscloses that stabilizers can be used to inhibit decomposition ofHCFO-1233zd during use. WO 2007/002625 discloses the use of varioustetrafluoropropenes in a variety of applications including heat transfersystems. The patent application discloses the stability of HFO-1234ze,HFO-1243zf, and HFO-1225ye with selected PAG lubricating oils andcompares the results to that of CFC-12 in a mineral oil, using theresults to state the refrigerants and compositions of that patentapplication have better stability than many commonly used refrigerants.

WO08027596, WO08027595, WO08027518, WO08027517, WO08027516, WO08027515,WO08027513, WO08027512, WO08027514 all are directed towards stabilizedsystems of fluoroolefins. These applications disclose that fluoroolefinscan exhibit degradation when exposed to high temperatures or whencontacted with other compounds e.g., moisture, oxygen, or othercompounds with which they may undergo condensation reactions. It isdisclosed that the degradation may occur when fluoroolefins are used asworking fluids in heat transfer equipment (refrigeration orair-conditioning equipment, for instance) or when used in some otherapplication. It is disclosed that because of the instability of thefluoroolefins, it may not be practical to incorporate thesefluoroolefins into refrigeration or air-conditioning systems. Therefore,to take advantage of the many other attributes of fluoroolefins, meansto reduce the degradation via the addition of a stabilizer is needed.

In the present invention, it was discovered that HCFO-1233zd (trans-and/or cis-isomers) and HCFO-1233xf are unexpectedly stable duringstorage and use without the need for an added stabilizer, being asstable or significantly more stable the many HCFCs and CFCs while beingmore environmentally sustainable.

SUMMARY OF THE INVENTION

The present invention relates to formulated systems of trans- and/orcis-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) and/or2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) that are sufficientlythermally and chemically stable such that they can be effectively usedwithout the need for additional stabilizers. The formulations of thepresent invention are particularly useful compositions forrefrigeration, heat transfer, and foam pre-mixes. Stability results forselect HCFCs are provided in “Chemical and Thermal Stability ofRefrigerant-Lubricant Mixtures with Metals”, by DF HuttenlocherSpauschus Inc., in DOE/CE/23810-5 (1992). The stated findings were thatR-123 is approximately ten times more stable than R-11, and that R-141band R-142b are more stable than R-123, EP0539719 discloses that R-141bshould be used with a stabilizer, such as alpha-methylstyrene, toinhibit the formation of the toxic byproduct 1-chloro-1-fluoroethylene(HCFO-1131a). The present inventors discovered that HCFO-1233zd, withoutany additional stabilizer, was at least as stable as R-141b, and byextension it is also more stable than R-123 and R-11.

DETAILED DESCRIPTION OF THE INVENTION

With continued regulatory pressure there is a growing need to identifymore environmentally sustainable replacements for refrigerants, heattransfer fluids, foam blowing agents, solvents, and aerosols with lowerozone depleting and global warming, potentials. Chlorofluorocarbon (CFC)and hydrochlorofluorocarbons (HCFC), widely used for these applications,are ozone depleting substances and are being phased out in accordancewith guidelines of the Montreal Protocol. Hydrofluorocarbons (HFC) are aleading replacement for CFCs and HCFCs in many applications; though theyare deemed “friendly” to the ozone layer they still generally possesshigh global warming potentials. One new class of compounds that has beenidentified to replace ozone depleting or high global warming substancesare halogenated olefins, such as hydrofluoroolefins (HFO) andhydrochlorofluoroolefins (HCFO). Because of the presence of alkenelinkage it is expected that the HFOs and HCFOs will be chemicallyunstable, relative to preceding HCFC or CFC. The inherent chemicalinstability of these materials in the lower atmosphere results in shortatmospheric lifetimes, which provide the low global warming potentialand zero or near zero ozone depletion properties desired. However, suchinherent instability is believed to also impact the commercialapplication of such materials, which may degrade during storage,handling and use, such as when exposed to high temperatures or whencontacted with other compounds e.g., moisture, oxygen, or othercompounds with which they may undergo condensation reactions. Thisdegradation may occur when halo-olefins are used as working fluids inheat transfer equipment (refrigeration or air-conditioning equipment,for instance) or when used in some other application. This degradationmay occur by any number of different mechanisms. In one instance, thedegradation may be caused by instability of the compounds at extremetemperatures. In other instances, the degradation may be caused byoxidation in the presence of air that has inadvertently leaked into thesystem. Whatever the cause of such degradation, because of theinstability of the halo-olefins, it may not be practical to incorporatethese halo-olefins into refrigeration or air-conditioning systems, or inother applications such as in foam polyol pre-mixes.

Good understanding of the chemical interactions of the refrigerant,lubricant, and metals in a refrigeration system is necessary fordesigning systems that are reliable and have a long service life.Incompatibility between the refrigerant and other components of orwithin a refrigeration or heat transfer system can lead to decompositionof the refrigerant, lubricant, and/or other components, the formation ofundesirable byproducts, corrosion or degradation of mechanical parts,loss of efficiency, or a general shortening of the service life of theequipment, refrigerant and/or lubricant.

In the present invention, it was discovered that the halogenated olefinsHCFO-1233zd and/or HCFO-1233xf are unexpectedly stable, sans additionalstabilizing agents, in systems typical of refrigeration, airconditioning, heat transfer systems, including within the presence oflubricants, metals, and moisture. It was discovered that halogenatedolefins HCFO-1233zd and/or HCFO-1233xf is at least if not more stablethan similar HCFC and CFC refrigerants, including R-141b, R-123, andR-11, and can therefore be particularly useful as a refrigerant or heattransfer fluid while providing both the benefits of an extended servicelife as well as greater environmental sustainability.

In a refrigeration, air conditioning, or heat transfer system,lubricating oil and refrigerant are expected to be in contact with eachother in at least some parts of the system, if not most of the system,as explained in the ASHRAE Handbook: HVAC Systems and Equipment.Therefore, whether the lubricant and refrigerant are added separately oras part of a pre-mixed package to a refrigeration, air conditioning, orheat transfer system, they are still expected to be in contact withinthe system and must therefore be compatible.

In one embodiment of the present invention, the stable halogenatedolefin systems are refrigeration, air conditioning, or heat transfersystems comprising chloro-3,3,3-trifluoropropene, preferably HCFO-1233Ain such a system the HCFO-1233zd will be in contact with various metalsand other components and must remain stable for extended operation.Typical materials which are present in such systems include steel,stainless steel, aluminum, iron, copper, and mixtures thereof. Inanother embodiment of the present invention said stable systems alsocomprising lubricants, including mineral oils, alkyl benzene oils,polyvinyl ether oils, polyol ester oils, polyalkylene glycol oils,poly(alphaolefin) oils, and mixtures thereof.

The stable halogenated olefin systems comprisingchloro-3,3,3-trifluoropropene, preferably1-chloro-3,3,3-trifluoropropene (R-1233zd),2-chloro-3,3,3-trifluoropropene (R-1233xf), and mixtures thereof, andeven more preferably trans-1-chloro-3,3,3-trifluoropropene are intendedto include new systems, servicing of existing systems, and retrofittingof existing systems. The preferred chloro-3,3,3-trifluoropropene istrans-1-chloro-3,3,3-trifluoropropene comprising greater than 70 wt %trans isomer. For example, due to the stability ofchloro-3,3,3-trifluoropropene with lubricants and metals,chloro-3,3,3-trifluoropropene can be used to service existing equipmentalready containing other refrigerants including, but not limited to,HCFC-123 and/or CFC-11, without worsening the system stability. This caninclude adding chloro-3,3,3-trifluoropropene, either alone or incombination with other refrigerants, to said existing equipment in orderto top-off a refrigerant charge or by removing part or all of saidexisting refrigerant and then replacing it withchloro-3,3,3-trifluoropropene, alone or in combination with otherrefrigerants.

Chloro-3,3,3-trifluoropropene can also be charged to new equipment,alone or in combination with other refrigerants such ashydrofluorocarbons, hydrochlorofluorocarbons, hydrofluoroolefins,hydrofluorochlorocarbons, hydrocarbons, hydrofluoroethers,fluoroketones, chlorofluorocarbons, trans-1,2-dichloroethylene, carbondioxide, ammonia, and mixtures thereof. Exemplary hydrofluorocarbonsinclude difluoromethane (HFC-32); 1-fluoroethane (HFC-161);1,1-difluoroethane (HFC-152a); 1,2-difluoroethane (HFC-152);1,1,1-trifluoroethane (HFC-143a); 1,1,2-trifluoroethane (HFC-143);1,1,1,2-tetrafluoroethane (HFC-134a); 1,1,2,2-tetrafluoroethane(HFC-134); 1,1,1,2,2-pentafluoroethane (HFC-125);1,1,1,3,3-pentafluoropropane (HFC-245fa); 1,1,2,2,3-pentafluoropropane(HFC-245ca); 1,1,1,2,3-pentafluoropropane (HFC-245eb);1,1,1,3,3,3-hexafluoropropane (HFC-236fa);1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea);1,1,1,3,3-pentafluorobutane (HFC-365mfc),1,1,1,2,3,4,4,5,5,5-decafluoropropane (HFC-4310), and mixtures thereof.Exemplary chlorofluorocarbons include trichlorofluoromethane (R-11),dichlorodifluoromethane (R-12), 1,1,2-trifluoro-1,2,2-trifluoroethane(R-113), 1,2-dichloro-1,1,2,2-tetrafluoroethane (R-114),chloro-pentafluoroethane (R-115) and mixtures thereof. Exemplaryhydrocarbons include propane, butane, isobutane, n-pentane, iso-pentane,neo-pentane, cyclopentane, and mixtures thereof. Exemplaryhydrofluoroolefins include 3,3,3-trifluoropropene (HFO-1234zf),E-1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene (HFO-1234yf),E-1,2,3,3,-pentafluoropropene (E-HFO-1255ye),Z-1,2,3,3,3-pentafluoropropene (Z-HFO-125ye),E-1,1,1,3,3,3-hexafluorobut-2-ene (E-HFO-1336mzz),Z-1,1,1,3,3,3-hexafluorobut-2-ene (Z-HFO-1336mzz),1,1,1,4,4,5,5,5-octafluoropent-2-ene (HFO-1438mzz) and mixtures thereof.Exemplary hydrofluoroethers include1,1,1,2,2,3,3-heptafluoro-3-methoxy-propane,1,1,1,2,2,3,3,4,4,-nonafluoro-4-methoxy-butane and mixtures thereof. Anexemplary fluoroketone is1,1,1,2,2,4,5,5,5-nonafluoro-4(trifluoromethyl)-3-3pentanone.

In another embodiment of the present invention, a stable pre-blendformulation can be prepared by mixing chloro-3,3,3-trifluoropropene,alone or in combination with other refrigerants, with a lubricant sansadditional stabilizer. The stable system refrigerant/lubricant pre-blendcan then be charged to a refrigeration, air conditioning, or heattransfer system.

For the production of polyurethane foams, it is typical to prepare apolyol pre-mixture (typically referred to as the B-side) that containsthe blowing agent. This B-side foam pre-mix will form foam when mixedwith a polymeric MDI mixture (typically referred to as the A-side). TheB-side foam pre-mix formulation must remain chemically and thermallystable before being mixed with the A-side formulation to preventproblems such as the creation of undesirable byproducts, decompositionof B-side components, undesired polymerization etc. These can decreasethe efficiency of the foaming formulation, produce toxic or reactivecomponents, produce more volatile components that could increase thepressure of the B-side container, etc. It was discovered in the presentinvention that HCFO-1233zd and/or HCFO-1233xf are unexpectedly stable inB-side polyol foam pre-mixes sans additional stabilizer, being at leastif not more stable than preceding HCFC blowing agents in polyol foampre-mixes, such as HCFC-141b. Foam pre-mixes containing HFCO-1233zdand/or HCFO-1233xf will bring the benefit of added shelf life comparedto pre-mixes of HCFC-141b.

The following non-limiting examples are hereby provided as reference:

EXAMPLES

The compatibility and stability of refrigerants in the presence oflubricating oils, moisture, and metals was tested at elevatedtemperatures in 300 mL stainless steel autoclaves. The 300 mL autoclaveswere first loaded with approximately 10 g of oil, 1 g of water, andcoupons or chips of active metals: aluminum, copper, and iron. To eachautoclave was added approximately 10 to 11 g of refrigerant,

The autoclaves were sealed and placed in a constant temperature oven at140° C. for 48 hours. After which the autoclaves were allowed to cooland then the vapor space was analyzed by gas chromatography (GC) tocheck for decomposition and identify degradation products.

In calculating the purity of the refrigerant, some of the impuritiescontained in the starting material were subtracted from the GC scans tobetter reflect changes in purity of the refrigerant and better identifythe appearance of degradation products.

Example 1

The compatibility and stability of trans-HCFO-1233zd in the presence oflubricating oils and metals was tested at elevated temperatures instainless steel autoclaves following the procedure described previously.The lubricants tested in three separate autoclaves were AB-150, MO-150,and POE-22. In a fourth autoclave, trans-HCFO-1233zd was tested withoutlubricant, moisture, or the metal chips to be used as a referencesample. The original HCFO-1233zd contained from I to 2% impurities,primarily HFO-1234ze and HFC-245fa, which were subtracted out of the GCscans as described previously.

Table 1 shows the purity of the samples following the stability tests.The purity of the HCFO-1233zd remained greater than 99% in all cases.The primary impurities in the samples containing oil were dimethylterephthalate and diethylphthalate which were not decomposition productsof the HCFO-1233zd.

Comparative Example 2

The compatibility and stability of HCFC-141b in the presence oflubricating oils and metals was tested at elevated temperatures instainless steel autoclaves following the procedure of example 1, exceptreplacing the HCFO-1233zd with HCFC-141b. The HCFC-141b containedapproximately 0.02% alpha-methylstyrene as a stabilizer. The HCFC-141btaken from the reference sample remained fairly pure at greater than99.9%. The HCFC-141b showed signs of significant decomposition when inthe presence of lubricating oils, metals, and moisture, with theappearance of numerous degradation products, such as1,1-dichloroethylene, and particularly with a significant increase inthe level of 1-chloro-1-fluoroethylene (HCFO-1131a), from less than 15ppm for the reference sample to over 1500 ppm or even over 3300 ppm forthe samples containing the oils. These results are shown in Table 1. Thestainless steel autoclaves containing lubricants showed significantdiscoloration (darkening) or corrosion in areas contacted by the othermetals. This corrosion could not be removed by simple scrubbing orwashing. Corrosion of this type was not observed in Example 1.Comparative Example 2 shows that HCFO-1233zd is at least as stable asHCFC-141b, even when the HCFC-141b is stabilized to inhibitdecomposition.

TABLE 1 Refrigerant purity following stability testing with lubricantsExample Refrigerant Reference AB-150 MO-150 POE-22 1 1233zd 99.97%99.43% 99.18% 99.59% 2 141b 99.98% 98.49% 99.07% 99.08% (1131a) (13 ppm)(~1500 ppm) (~3300 ppm) (~1800 ppm)

Examples 3 and 4 and Comparative Examples 5 and 6

The compatibility and stability of trans-HCFO-1233zd and HCFC-141b weretested in the presence of lubricating oils similar to as in Example 1and comparative example 3, with the following modifications: In examples3 and 4, two autoclaves were prepared with HCFO-1233zd with MO-150 andPOE-22 respectively, as was done in example 1. In comparative examples 5and 6, two autoclaves were prepared with HCFC-141b, containingalpha-methylstyrene as a stabilizer, with MO-150 and POE-22respectively, as was done in comparative example 2. The autoclaves weremaintained at 140° C.; for 96 hours, instead of 48 hours. The vaporspace of each autoclave was sampled and tested by GC/MS both before andafter the stability tests. The results are shown in Table 2.

The purity of the HCFO-1233zd changed by only 0.03% or less while thepurity of the HCFC-141b changed by greater than 0.3%. The primarydecomposition byproduct for HCFO-141b was HCFO-1131a, increasing from 11ppm to over 1400 ppm.

TABLE 2 Refrigerant purity following stability testing with lubricantsPurity Example Refrigerant Oil: Before After Change 3 HCFO-1233zd MO-15099.99% 99.98% 0.01% 4 HCFO-1233zd POE-22 99.97% 99.94% 0.03% HCFC-141bMO-150 99.95% 99.64% 0.31% (1131a) (11 ppm) (~1900 ppm) 6 HCFC-141bPOE-22 99.71% 98.97% 0.74% (1131a) (11 ppm) (~1400 ppm)

Example 7

A sample of HCFO-1233zd, containing trans- and cis-isomers in a ratio ofapproximately 7:3, was stored in a clear glass vial for over ten yearsin uncontrolled ambient conditions. Following the storage period thesample was visually observed and tested by GC analysis. The sample stilllooked clear and unchanged and GC analysis showed no significant changein sample composition. This example shows that HCFO-1233zd is stableduring extended storage conditions.

Comparative Example 8

A sample of R-11 from 1981 was stored in a 30 gallon steel drum.Following the storage period, the sample had turned yellow and emitted astrong odor. This example shows that HCFO-1233zd will be more stablethan R-11 in storage and in use, especially in the presence of activemetals, lubricants, and moisture.

Example 9 and Comparative Example 10

The chemical and thermal stability of HCFO-1233zd and HFO-1234ze B-sidepolyol formulations were tested in stainless steel autoclaves asfollows:

Each foam pre-mix formulation was loaded into a 300 mL stainless steelautoclave. The autoclaves were heated in a constant temperature oven for24 hours at 100° C. The autoclaves were then removed from the oven andkept at ambient temperature for 72 hours, after which for each a sampleof the vapor space composition was collected into a Tedlar® GC samplebag for subsequent analysis by GC/MS.

To each autoclave was added the base B-side formulation shown in Table3:

TABLE 3 B-side formulation B-Side Parts Wt % B Jeftol SG-360 35.0 39.2sucrose polyol Jeffol R-425-X 10.0 11.2 mannich polyol SF-265 20.0 22.4triethanol amine polyol DEG 5.0 5.6 diethylene glycol Dabco 33-LV 0.50.6 amine catalyst Jeffcat ZR-70 0.5 0.6 amine catalyst Tegostab B 84652.1 2.4 siloxane based surfactant NP 9.5 15.1 16.9 nonpehnol Added water1.0 1.1 Total (w/o blowing 89.2 100% agent)Foam pre-mix formulations were then prepared by adding the blowingagents to the B-side formulations at a loading of 25 parts blowing agentto 75 parts B-side. One foam pre-mix formulation was prepared withHCFO-1233zd, example 9, and another with HFO-1234ze, comparative example10. The foam pre-mix formulations were then subjected to the stabilitytest.

The GC/MS analysis of the vapor phase composition of example 9 showed nosignificant degradation in the HCFO-1233zd. Most degradation byproductswere attributable to decomposition of HFO-1234ze, which was present atabout 2% of the original HCFO-1233zd sample.

The HFO-1234ze of comparative example 10 showed more significantdecomposition as shown by the GC/MS data provided in Table 4. Thepresence of the fluorinated silane products came from evolution of HITfrom trans-HFO-1234ze, which in turn can react with more HFO-1234ze toyield HFC-245a and with the siloxane-based surfactants used in theformulation:CF₃—CH═CHF→CF₃—C≡CH+HF  1)HF+SiMe₃(OsiMe₂)nOSiMe₃→SiFMe₃ +nSiF₂Me₂+H₂O  2)

TABLE 4 Vapor analysis of Comparative Example 10 GC Area % original1234ze After aging trans-HFO-1234ze 99.963 97.97 HFC-245fa 0 0.10Difluorodimethyl silane 0 1.50 Fluorotrimethyl silane 0 0.17Example 9 and comparative example 10 show that trans-HCFO-1233zd wasmore stable than the analogous hydrofluoroolefin trans-HFO-1234ze.

These examples show that chloro-3,3,3-trifluoropropenes, particularlyHCFO-1233zd, are unexpectedly stable during both storage and use and atleast as stable as prior HCFCs and CFCs, especially in combination withlubricants, moisture, active metals, polyol B-side formulations andmixtures thereof.

The invention claimed is:
 1. A polyol B-side composition comprisingpolyol, catalyst, surfactant and a blowing agent composition comprisingthe halogenated olefin 1-chloro-3,3,3-trifluoropropene and less thanabout 2% of impurities selected from the group consisting of HFO-1234ze,HFC-245fa and mixtures thereof wherein more than about 99 wt % of saidhalogenated olefin remains after exposure of said composition totemperature of 100° C. for 24 hours.
 2. The polyol B-side composition ofclaim 1 wherein said 1-chloro-3,3,3-trifluoropropene is predominantlytrans-1-chloro-3,3,3-trifluoropropene.
 3. The polyol B-side compositionof claim 1 wherein said 1-chloro-3,3,3-trifluoropropene is greater thanabout 70% trans-1-chloro-3,3,3-trifluoropropene.
 4. The polyol B-sidecomposition of claim 1 wherein said 1-chloro-3,3,3-trifluoropropene isconsists essentially of trans-1-chloro-3,3,3-trifluoropropene.
 5. Thepolyol B-side composition of claim 1 further comprising a componentselected from the group consisting of hydrofluorocarbons,hydrochlorofluorocarbons, hydrofluoroolefins, hydrofluorochlorocarbons,hydrocarbons, hydrofluoroethers, fluoroketones, chlorofluorocarbons,trans-1,2-dichloroethylene, carbon dioxide, ammonia, and mixturesthereof.
 6. The polyol B-side composition of claim 5 wherein saidhydrofluorocarbon is selected from the group consisting ofdifluoromethane (HFC-32); 1-fluoroethane (HFC-161); 1,1-difluoroethane(HFC-152a); 1,2-difluoroethane (HFC-152); 1,1,1-trifluoroethane(HFC-143a); 1,1,2-trifluoroethane (HFC-143); 1,1,1,2-tetrafluoroethane(HFC-134a); 1,1,2,2-tetrafluoroethane (HFC-134);1,1,1,2,2-pentafluoroethane (HFC-125); 1,1,1,3,3-pentafluoropropane(HFC-245fa); 1,1,2,2,3-pentafluoropropane (HFC-245ca);1,1,1,2,3-pentafluoropropane (HFC-245eb); 1,1,1,3,3,3-hexafluoropropane(HFC-236fa); 1,1,1,2,3,3-heptafluoropropane (HFC-227ea);1,1,1,3,3-pentafluorobutane (HFC-365mfc),1,1,1,2,3,4,4,5,5,5-decafluoropropane (HFC-4310), and mixtures thereof.7. The polyol B-side composition of claim 5 wherein saidhydrochlorofluorocarbon is selected from the group consisting ofchlorodifluoromethane (HCFC-22), 1,1-dichloro-2,2,2-trifluoroethane(HCFC-123), 1-chloro-2,2,2-trifluoroethane (HCFC-124),1,1-dichloro-1-fluoroethane (HCFC-141b), 1-chloro-1,1-difluoroethane(HCFC-142b), and mixtures thereof.
 8. The polyol B-side composition ofclaim 5 wherein said chlorofluorocarbon is selected from the groupconsisting of trichlorofluoromethane (R-11), dichlorodifluoromethane(R-12), 1,1,2-trifluoro-1,2,2-trifluoroethane (R-113),1,2-dichloro-1,1,2,2-tetrafluoroethane (R-114), chloro-pentafluoroethane(R-115) and mixtures thereof.
 9. The polyol B-side composition of claim5 wherein said hydrocarbon is selected from the group consisting ofpropane, butane, isobutane, n-pentane, iso-pentane, neo-pentane,cyclopentane, and mixtures thereof.
 10. The polyol B-side composition ofclaim 5 wherein said hydrofluoroolefin is selected from the groupconsisting of 3,3,3-trifluoropropene (HFO-1234zf),E-1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene (HFO-1234yf),E-1,2,3,3,-pentafluoropropene (E-HFO-1255ye),Z-1,2,3,3,3-pentafluoropropene (Z-HFO-125ye),E-1,1,1,3,3,3-hexafluorobut-2-ene (E-HFO-1336mzz),Z-1,1,1,3,3,3-hexafluorobut-2-ene (Z-HFO-1336mzz),1,1,1,4,4,5,5,5-octafluoropent-2-ene (HFO-1438mzz) and mixtures thereof.11. The polyol B-side composition of claim 5 wherein saidhydrofluoroether is 1,1,1,2,2,3,3-heptafluoro-3-methoxy-propane,1,1,1,2,2,3,3,4,4,-nonafluoro-4-methoxy-butane and mixtures thereof. 12.The polyol B-side composition of claim 5 wherein said fluoroketone is1,1,1,2,2,4,5,5,5-nonafluoro-4(trifluoromethyl)-3-3pentanone.